United States Patent (19) 11, 3,960,807

McTaggart (45) June 1, 1976

54 THERMOFORMED POLYESTER ARTICLES 3,578,730 5/1971 Herwig et al....................... 260/873
HAVING IMPACT RESISTANCE AND HIGH 3,657,389 4/1972 Caldwell et al..................... 260/873
TEMPERATURE DIMENSIONAL 3,706,699 12/1972 Conix et al..................... 260/873 X
STABILITY FOREIGN PATENTS OR APPLICATIONS
75 Inventor: Larry S. McTaggart, St. Paul, Minn. l, 182,820 12/1965 Germany............................ 260/873
73) Assignee: Minnesota Mining and OTHER PUBLICATIONS
Manufacturing Company, St. Paul, Elwnyn Jones, “Thermoforming', Mod. Plast. Ency.
Minn. 1970-1971, vol. 47: No. 10A (Oct. 1970) pp. 602 and
(22 Filed: Sept. 30, 1974 604.
21 Appl. No.: 510,451 Primary Examiner-Donald E. Czaja
Assistant Examiner-S. M. Person
52 U.S. Cl................................ 260/40 R; 260/873 Attorney, Agent, or Firm-Alexander, Sell, Steldt &
(51 Int. Cl.’.......................................... C08L 67/02 Delahunt
58) Field of Search............ 260/873, 40 R, DIG. 35
57 ABSTRACT
(56) References Cited Shaped, thinwalled, thermoformed, heat-set polyester
UNITED STATES PATENTS articles having a composition comprising polyester,
3,405, 198 10/1968 Rein et al........................... 260/873 2-1.6% polymeric crack stopping agent, and at least
3,429,854 2/1969 Siggel et al..... ... 264/92 0.01% nucleating agent, exhibit relatively high tem
3496, 43 2/1970 Siggel et al........................... 264/92 perature dimensional stability and impact resistance.
3,504,080 3/1970 Siggel et al..................... 26O1873 X
3,562,200 2/1971 Jones et al........................ 260/40 R 9 Claims, No Drawings
 3,960,807
1. 2
contain at least three ingredients. The first ingredient is
THERMOFORMED POLYESTER ARTICLES the polyester itself, the second is a crack-stopping
HAVING IMPACT RESISTANCE AND HIGH agent, and the third is a nucleating agent.
TEMPERATURE DIMENSIONAL STABILITY The polyester materials themselves must be thermo
plastic, crystallizable or crystalline, have a glass transi
Thermoplastic polyester materials have been used for tion temperature (T) of at least 50° C. and a melting
the manufacture of a broad range of articles because of point of at least 150°C. The more preferred polyesters
their strength and flexural characteristics and high will have a melting point of at least 200° C. Many such
temperature stability. Fabrics and films are among the polyesters are described in U.S. Pat. Nos. 2,891,928;
more common articles produced with polyesters. Cer 10 3,048,564; 2,974, 122; 2,938,015; and 2,465,319. The
tain physical characteristics of polyesters in general most preferred polyester is polyethylene terephthalate.
have limited their use in certain processing areas such The polyesters used in accordance with the practice
as injection molding. Polyesters generally must be heat of the present invention are obtained by known poly
set for the product to have a reasonable degree of heat merization techniques from aromatic dicarboxylic
stability, and this heat setting step adds greatly to the 15 acids, preferably the lower alkyl esters thereof such as
working time for heat stable polyester products. Espe the dimethyl ester of terephthalic acid. The aromatic
cially when making shaped, thin-walled articles of man dicarboxylic acid or its ester or anhydride is esterified
ufacture, it is difficult to develop a full range of useful or transesterified and polycondensed with a saturated
properties including high temperature dimensional diol such as ethylene glycol. The saturated diols are
stability, tensile strength and flexural strength. 20
saturated aliphatic, cyclo-aliphatic, or aromatic diols,
Many different types of processes are avaliable for preferably the lower alkane-diols such as ethylene gly
shaping thermoplastic articles, such as injection mold col. Polyethylene terephthalate and other film-forming
ing, embossing, extruding, and thermoforming. All of polyesters within the definition are described in the art
these processes have some similar aspects, but in gen such as, for example, “Polyesters and Their Applica
eral are significantly different from each other both in 25 tions' by Bjorkstn et al., Reinhold Publishing Corp.
physical characteristics of the process itself and in the (1956), pp. 199-207. Mixtures of aliphatic carboxylic
properties of the finished article. Injection molding acids and saturated diols may be used also, but the
requires the use of fluidized polymeric material (such above described physical properties (i.e., melting point
as molten polymer or finely pelletized molding parti and glass transition temperature must be satisfied. Even
cles) injected into a shaped mold. There is very little in 30 some degree of three-dimensional bonding (cross-link
the process itself which orients or strengthens the poly ing) may be tolerated as long as these physical proper
meric material if it is capable of orientation. Embossing ties are maintained in the polyester component.
is the forceful impression of a surface design upon a The polyesters used in this thermoforming composi
preformed polymeric material, which will generally tion should also have at least a certain molecular
affect only the surface characteristics of the material 35
embossed. Extrusion is the forced flow of conformable weight in order to obtain desired flexural characteris
material through a shaped orifice, and is a very limited tics and for the crack stopping agent (later defined
process in that the shapes which may be produced are herein) to work effectively. The polyester comprises
substantially limited to elongate shapes with shaping in about 79-98% by total weight of the formulations used
only two dimensions (the dimensions of the orifice). 40 in the practice of this invention. A single polyester
Thermoforming is the application of shaping pressure material need not be used, but copolyesters, blends,
and heat to a preformed structure (generally a film or etc. may be used. In terms of its intrinsic viscosity
sheet formed by ordinary processing techniques) to (I.V.), the polyester should have an I.V. of at least
give a desired, three-dimensional shape to the struc 45 about 0.75. Preferably, the minimum intrinsic viscosity
ture. Each of these processes tends to require different will be about 0.80, and the most preferred polyesters
properties in the materials worked upon in order to will be at least 0.85. Polyesters are known to be ther
obtain the best results from a given process. moformed, as in the formation of packages for cold
This invention is related to the manufacture of inex storage of food; however, these packages are consis
pensive, shaped, thin-walled polyester goods having tently thermoformed from biaxially oriented sheets
heat stability, tensile strength and flexibility. 50 having an I.V. of from 0.55 to at most 0.70. Biaxially
This invention further relates to a thermoforming oriented materials cannot easily form articles having
process for producing such thin-walled polyester wall thicknesses of greater than 5 mils because of the
goods. great difficulty in drawing films of sufficient thickness
This invention also relates to particular polyester to result in drawn products of those relatively large
compositions which are thermoformed to produce thin 55 dimensions. These drawn films will also tend to shrink
walled polyester goods. at elevated temperatures.
In general with polyester materials, higher molecular Scrap polyester material may also be used in forming
weights, as measured by increased intrinsic viscosities the shaped compositions of this invention. Scrap poly
tend to display greater strength than lower molecular ester typically has an I.V. of 0.45-0.80 depending on
weight polyesters. When working with moderate and 60 the starting I.V. and the extent of thermal degradation
high molecular weight polyesters, higher crystallinity is in prior film or fiber processing. In the practice of this
used to increase tensile strength; however, flexural invention polyethylene terephthalate (PET) must be
properties then diminish and the polyester become stiff repolymerized to an I.V. of at least 0.75 to obtain any
and brittle. For any particular use of polyesters, there effect from the crack stopping agent with I.V.'s ap
fore, the particular composition of materials and pa 65 proaching 1.0 desired. Repolymerization is best accom
rameters must be carefully selected. The formulation of plished by solid state polymerization (SSP) in which
the polyester thermoforming composition used is espe particles of resin are heated up to within 5-10°F of
cially critical to the practice of this invention and must their melting point while engulfed in a stream of heated
 3,960,807
3 4
inert gas. Polymerization rates of 0.05 I.V. unit/hr. or polycarbonates, polysulfones, certain polyesters, and
more are readily obtained. natural and synthetic rubbers.
It is important that the inert gas for scrubbing the Crack-stopping agents are further defined by a sim
reaction products be free of moisture and oxygen to ple test. A 20 mil polyester film material of substan
obtain rapid polymerization rates and prevent develop tially 100% polyethylene terephthalate having 35%
ment of an amber color in the resin. crystallinity and 0.65 intrinsic viscosity is subjected to
The intrinsic viscosity of the polyester is a standard the flex test hereinafter defined. Any polymeric mate
by which the degree of polymerization of the polyester rial which, when blended with the polyester film mate
is indicated and is a value that is defined by the formula rial in an amount 10% by total weight of the composi
10 tion and formed into a film and subjected to the flex
test, increases the flex life of the film by 20% is a crack
lim in Nr
stopping agent in the practice of this invention.
n = C - O C
The third necessary component of the polyester ther
moforming composition is a nucleating agent. Nucleat
15 ing agents are well known in the polyester art as materi
where Nr is the ratio at 30°C of the viscosity of a dilute als which accelerate crystallization which is necessary
solution of the polyester dissolved in trifluoroacetic to obtain thermal dimensional stability (see U.S. Pat.
acid to the viscosity of the trifluoroacetic acid itself and Nos. 336 1848; 3,405, 198; 3,562,200; 3,564,077; and
C represents the concentration of the dilute solution, 3,565,852; and Netherlands Pat. No. 65/l 1744). These
the unit being the number of grams of the polyethylene nucleating agents may be, for example, talc, gypsum,
terephthalate in 100 cc of the solution. silica, calcium carbonate, alumina, titanium dioxide,
Articles produced from low molecular weight (I.V. alumina and calcium silicate, pyrophylite, finely di
0.50 or less) polyethylene terephthalate display poor vided metals, powdered glass, carbon black, graphite,
mechanical properties and as the I.V. is increased, a 25
etc., individually or as mixtures of one or more. The
general improvement is obtained. Unfortunately, even minimum effective concentration is 0.01% by weight of
when I.V. is increased to levels that are impractical for polyester. The particle diameter should be less than 50
processing, polyethylene terephthalate does not de microns and is preferred below 10 microns. In the prac
velop totally satisfactory fracture characteristics. Con tice of this invention, titanium dioxide having a particle
trol of intrinsic viscosity alone does not yield satisfac diameter of 0.2–3.5 microns is most preferred. The
tory mechanical properties. Certain aspects of the solid 30 nucleating agent, as in the case of titanium dioxide may
state polymerization process utilized in this work are be used in sufficient quantities (past 5% of total
detailed in the following patents: U.S. Pat. Nos. weight) so that it acts as pigmentation for the composi
3,075,952; 3,344,091; and British Pat. No. 1,066,162. tion as well as a nucleating agent. Separate coloring
A second component of these thermoforming polyes material may, of course, be added.
ter composition materials is a polymeric material which 35 The nucleating agent may be used to an upper limit
is blended with the polyester. This second polymeric of 20% in the compositions thermoformed herein in the
material is a crack stopping agent. The crack stopping practice of this invention. It is preferred to use no more
agent is a material which retards the growth, propoga than 10% by total weight of the composition as the
tion or formation of cracks during mechanical failure addition of materials above 10% and up to 20% does
40 not improve the properties of the article, and to Some
of brittle polymers. Such failure readily occurs during degree adverse effects may be encountered such as
handling by production apparatus and, in the case of increased brittleness. The 5% preferred limit is based
food trays, during high speed Stacking and transporting. upon the fact that the increasing amount of nucleating
There is much technology which has been developed in agents up to 10% do not significantly improve proper
the use of these agents for particular effects upon poly 45 ties, although with the proper selection of nucleating
esters, and the materials are commercially available. agent the cost of the articles may be lowered. Both
U.S. Pat. No. 2,405, 198 describes polyethylene, poly inorganic and organic nucleating agents as known in
propylene and poly(4-methylpentene) as improving the art may be used as they are functionally equivalent,
impact strength; U.S. Pat. No. 3,361,848 additionally however, inorganic nucleating agents are preferred
shows polyisopropylene, polybutene and polypentene because of their generally lower costs.
for similar purposes. Other art of significant interest is The particular articles of manufacture which this
U.S. Pat. Nos. 3,579,729 and 3,562,200 and articles invention concerns are thin-walled thermoformed poly
such as “Two Phase Polymer Systems' by S. L. Posen, ester articles. By thin-walled it is meant that the articles
Polymer Engineering and Science, April, 1966 pp. may not have a thickness exceeding 40 mils. In a pre
115-123 and Polymer Structure Properties and Applica 55 ferred embodiment of this invention, the wall thickness
tions by R. D. Deanin, Cahners Pub. Co., 1972. The should not be greater than 25 mils. These thin-walled
additives discussed and reviewed there in function as articles are formed from preformed film materials
crack stopping agents. This crack Stopping agent which are shaped under heat and pressure to conform
should be present in at least 2% by weight of polyester to a desired form. In particular, the thin-walled articles
up to 16% by weight of the total composition. The 60 of this invention are shaped meaning that the thermo
preferred range is 5-10% by weight. A preferred class forming process causes at least 10% and preferably at
of crack stopping agents are the polyolefin agents, least 20 or 25% of the weight of the starting sheet com
especially polyethylene. The most preferred crack position to deform out of the plane of the starting sheet.
stopping agent is TPX (a registered trademark of I.C.I. This invention is particularly suitable for the manufac
and comprises poly-4-methylpentene-1). 65 ture of thin-walled trays having a generally flat interior
Other classes of polymeric materials which are or central portion and a raised enclosing edge portion
known to contain particular species useful as crack to surround and restrain materials placed on the inter
stopping agents are the polyamides (e.g., nylon–6,6), ior. The transition from the center to the raised portion
 3,960,807
S 6
may be a sharply defined right angle corner, but is by total weight “TPX' and 1% TiO2. Composition B
preferably, a smooth arcuate transition. The sheet is comprised 89% of the polyester, 10% “TPX' and 1%
deformed such that the edge area is higher at every TiO2. Test samples of each of these compositions were
point then the central area, and there are no seams or formed by injection molding and thermoforming. The
welds on the edge. In the formation of trays, particular samples were injection molded into 3 inch discs having
design features such as raised partitions in the central a thickness of 20 mils by preblending the components
portion of the tray or container may be formed as de and melting them in the barrel of an injection molder.
sired by selecting the appropriate thermoforming mold. The injection molder was set at an injection cycle of 8
The trays or cartons formed in the practice of this
O
seconds. The mold was operated at a temperature of
invention find particularly good utility as containers for 149°C and the discs were held in the mold for 1 minute.
food to be heated in hot air, steam, autoclave, infrared, The 3 inch thermoformed discs were produced by ther
or microwave ovens because of their ability to retain moforming trays from an extruded sheet of these com
dimensional stability at high temperatures. positions, and cutting discs from the flat bottom section
The trays presently in general use suffer from a num of the trays. The extruded film, a 20 mil sheet, was
ber of deficiencies which render them unsatisfactory 5 heated to 121°C and thermoformed with applied vac
for at least some of the potential uses for food trays. uum in a rectangular aluminum mold having 5 X 8 X 1
Three major classes of materials are used for forming inch width, length and depth dimensions respectively.
trays, simple thermoplastic materials (e.g., polyethy The mold temperature was raised to 149°C and the
lene, polypropylene, polystyrene, and polyvinyl chlor thermoformed tray was restrained in the mold with
ide), aluminum sheeting, and thermoset resins (e.g., vacuum for 1 minute. These discs, differing only in
the melamines). The thermoplastic materials may be their process of manufacture were then subjected to
used only for limited temperature ranges (usually not procedures to test the physical properties of the discs.
higher than 100°C) before their dimensional stability The testing procedure was ASTM D-2 176-69 with
diminishes, even though these materials have sufficient 25
1.5 kg loading. The jaws were spaced to accommodate
impact strength for mechanical handling. Aluminum the thickness used during the test. The test procedure is
tends to have sharp edges, dents easily, and cannot be to repeatedly flex the film 135 in one direction and
used in microwave apparatus. The thermoset resins then the other direction to constitute a single flex. The
especially the widely used melamines, have poor im flex number indicates the number of flexes to break.
pact strength, are brittle, tend to give off odors when This test is also known as the M.I.T. fold endurance
heated and are rather expensive. The thermoformed 30 test. The results are tabulated below.
polyester compositions of this invention suffer from
none of the above-mentioned deficiencies.
In the formation of thin-walled shaped articles having Compo-
Injection Molded
Flexes to Compo-
Thermoformed
Flexes to
any significant deviation from a planar form, and even sition Aging Break sition Aging Break
when forming thin-walled sheets of polyesters, injec 35
A 204°C all A 204°C 1468
tion molding is an unsatisfactory technique, the injec for samples for 9,853
tion molding process itself acts to produce properties in 60 mins broke or 60 mins (),902
the article which are not desirable. For example, be cracked 10,864
on first 5,888
cause the surface areas of the opposite faces of the flex 13,909
mold must be relatively close in forming articles of less 40 A d al A t
10,864
7882
than 40 mils, especially below 30 mils, differential cool aged samples aged 1 ()()3
ing of the polymeric material causes layering within the broke or
cracked
314
4,323
article. This produces a lack of uniform properties and on first 33,902
creates intolerable lines of weakness at the interphase 45 flex 15,397
of the layers. The surfaces closest to the nozzle solidify B 204°C
for
al
samples
B 204°C
for
1872
6.86
first, cooling even during that part of the process when 60 mins broke or 60 mins 94.
polymeric material is still being forced into the mold. cracked
on first
1965
9,093
This causes the layering as well as the formation of flow flex 1403
patterns and lines of stress in the product which tend to 50 B not 883 B not 7,512
give undesirable directional mechanical properties to. aged 14 aged 37, 52
2,57 6,523
the product. For example, upon impact hardness test 1 1,735
ing, injection molded thin-walled polyester materials 63,568
(),895
will generally tend to crack along the flow lines re 38,549
tained in the material from their manufacture. These
problems have been found to be obviated in the forma 55 "It is believed that faulty test procedures led to this extreme value.
tion of thin-walled polyester materials through the use
of thermoforming processes. , It can readily be seen from the above data that the
The following tests were performed in order to show thin-walled articles of those compositions produced by
the differences in physical properties between thin thermoforming show a substantially improved flex-life
walled materials formed by thermoforming and thin 60 when compared to thin-walled articles produced by
walled materials formed by injection molding. All injection molding.
weight percentages are based on the total weight of the EXAMPLE 2
composition.
EXAMPLE I The impact properties of the 20 mil thick discs pro
65 duced by the two different processes were examined
Two polyester thermoforming compositions Were according to the following test procedures.
formulated. Composition A comprised 94 parts of an The impact specimens were clamped between two 5
ethylene glycol dimethyl terephthalate polyester, 5% X 6 inch metal plates/8 inch thick which had a 2% inch
 3,960,807
7 8
diameter circle cut from their centers. The specimens detail. The sheet was cut to 9 X 9 inch dimensions,
were centered about the holes and steel balls dropped placed in vacuum former, heated to 121°C and vacuum
onto the center of the exposed specimens. The size of formed into the 5 X 8 x 1 inch oval shaped dish. The
the steel ball and the height from which the ball was armorphous dish was restrained with vacuum in the
dropped to produce failure were recorded. Because of 5 same mold at a temperature of 149°C for 1 minute to
size limitations in the testing apparatus, the greatest effect crystallinity. A four oz. piece of precooked
impact which could be demonstrated was a 1 % inch chicken and four oz. of corn were packaged in a num
steel ball dropped from a height of 21 inches. The ber of trays and were frozen at -18°C. Later, trays were
testing results were as follows: removed from the freezer and dropped repeatedly to
Injection Molded Thermoformed
Comp. Aging Ball* Height Comp. Aging 3:* Height
inches inches inches inches
diam. diam.
A not la 6 A () the no breakage
occurrel in
34 any thermo
formed speci
a 2 B k) men with A.''
or 1%' balls
3 () A. dropped from 21
inches
a 2 A 400
60 min.
A 400°F %
60 min.
a 2 B 4) OF
60 min.
B 40(). 34
60 min.
a.
*Bat weights:
1% inches. 286.5 grin: 'a inches. 205.5 gin; % inch. 18.7gm: A. inch, 8.3 grin.
Again it can be readily seen that the thermoformed
specimens displayed substantially better impact resis the floor from a distance of four feet with no apparent
tance than the injection molded specimens. damage to the dish. Additional dishes were reconsti
In thermoforming the compositions used in this in tuted in conventional ovens at an oven setting of 190°C
vention, ordinary thermoforming techniques known in for 30 minutes and in a microwave oven for 3 minutes
the art may be used. The temperatures, pressures and to attain a serving temperature of 65°C. The food was
processing times are dependent upon the properties palatable and no undesirable effects were observed for
desired in the final article. For certain compositions, a the oven dishes.
minimum temperature of 50°C may be used, although 35 I claim:
higher temperatures are generally preferred. In the 1. A shaped, thin-walled, thermoformed, heat-set
most preferred composition used in the practice of this polyester article the composition of which comprises:
invention (polyethylene terephthalate, poly-4-methyl A. a thermoplastic, crystallizable, polyester having a
pentene-1, and TiO), temperatures on the order of glass transition temperature of at least 50°C and a
121°C are preferred. The upper temperature limit is the 40 melting point of at least 149°C and an intrinsic
melting point of the thermoforming composition. viscosity of at least 0.75,
After the forming process, the article is annealed or B. from 2-16% of a polymeric crack stopping agent,
heat-set under restraint. The annealing or heat-setting and
is the known technique of heating the article so as to C. from 0.01% to 20% by weight of a nucleating
develop the crystallinity. This is performed while the 45 agent.
article is restrained, preferably in the mold itself, so 2. The polyester article of claim 1 wherein the poly
that its desired shape is maintained. This heat setting ester is polyethylene terephthalate.
must be done at least 93C and preferably between 3. The polyester article of claim 2 wherein the crack
135°C-190°C. The heat setting conditions should be stopping agent is a polyolefinic material.
selected on the basis of the appropriate degree of crys SO 4. The polyester article of claim 2 wherein the crack
tallinity desired. With the preferred composition of this stopping agent comprises poly-4-methylpentene-l.
invention 135°C-190°C for 3 minutes to 20 seconds 5. The polyester article of claim 4 wherein the nucle
respectively are effective conditions. ating agent is titanium dioxide in a concentration of
EXAMPLE 3 0.01% to 5% by weight of the composition.
55 6. The polyester article of claim 1 having the shape of
100 lbs. of polyethylene terephthalate with an I.V. of a tray with a generally flat central portion and raised
0.77 was placed in a chamber and heated in a fluid bed edges.
at 24.6°C with a dry nitrogen gas stream. Heating was 7. The polyester article of claim 5 having the shape of
continued for eight hours after which the resin was 60 a tray with a generally flat central portion and raised
cooled to room temperature while still in the inert gas edges.
stream. The I.V. of the solid state polymerized resin 8. A method of producing the article of claim 1 which
was 1.26. After appropriate drying, 10%. ICI TPX (RT comprises blending components A, B, and C, forming a
18) and 1% TiO (TiPure R-900) were blended with sheet from the blended components, and thermoform
89% of the polyethylene terephthalate resin and ex ing the sheet into its desired shaped, and heat-setting
truded into 20 mil sheet of 9 inch width. 65 the formed product.
The sheet was rapidly quenched to prevent any crys 9. The polyester article of claim 1 having a thickness
tallization which requires greater force at the time of of 10-40 mils.
forming and limits the depth of draw and replication of